Lecture 11: Homogeneous Nucleation: solid-solid phase transformation Today’s topics • Homogeneous nucleation for solid-solid phase transformation, and the major difference compared to the liquid-solid phase transformation: the role played by the strain energy due to the deformation caused by the phase transformation. • Strain energy --- the factor determining the hysteresis in phase transformation, i.e., supercooling (under) or superheating (above) the equilibrium temperature. Briefly in last Lecture 10: For a particle formation, the free energy change ΔG(r) is balanced by the two ‘competitive’ factors, the volume free energy and interfacial energy due to formation of solid phase, just as depicted in the diagram below. (r) r0 (r) The nucleation barrier, 16πγ 3 2γ = ΔG* = ΔG(r*) 2 ; r* = − 3∆GV ∆GV Today’s lecture: ΔGV can be expressed as : 1 0 0 1 001 0 0 0 0 ΔGV = (µs − µl ) = ()GGsl− = [H s − TSs − Hl + TSl ] VM VM VM 1 1 0 0 0 0 = [T(Sl − Ss ) − (Hl − H s )] VM 0 0 0 0 At T=TM, µl (TM) = µs (TM), or Gl (TM) = Gs (TM) due to the solid-liquid equilibrium, then 0 0 0 0 0 0 0 0 Hl - TM Sl = Hs - TM Ss Hl – Hs = TM (Sl -Ss ), replace this into the Eq of ΔGV, we have 1 0 0 0 0 ΔGV = [T (Sl − Ss ) − TM (Sl − Ss )] VM 1 0 0 = (Sl − Ss )(T − TM ) VM 00 SSsl− Lets define ΔSV = , then, ΔGV = - ΔSVΔT VM 0 0 Since Sl > Ss , thus ΔSV <0, and since ΔT = T - TM < 0, we have ΔGV = - ΔSVΔT<0 Also by replacing ΔGV into the equation of ΔG*, we have 3 2 2 ΔG* = 16пγ /3(ΔSV) (ΔT) As T TM, ΔT 0, then ΔG*—>∞, barrier for nucleation is infinite at TM. This implies that supercooling is needed for Homogeneous nucleation. For example, a liquid nickel can be o supercooled by 250K below TM (1453 C) without solidification, or pure water can be supercooled to as low as -42 oC without being frozen into ice. A special case: Homogeneous nucleation in a solid-solid phase transformation In a solid-solid transformation, a small change in specific volume that occurs must be accommodated elastically, leading to strain energy effect. Such a strain energy change must be included, together with the volume free energy and interfacial energy changes (as described for the liquid-to-solid transformation), into the free energy change of a solid-solid transformation, 4π ΔG(r) = r3∆G + 4πr2 γ + strain energy 3 V Now lets derive the strain energy Consider α—>β solid-solid transformation as depicted below 2 G or µ β α T T Teq β α Assuming VM >VM , when a β particle of radius r forms in α matrix, both particle and matrix must deform elastically to accommodate the phase transformation. The formation of such coherent interface raises the free energy of the system on accounted of the elastic strain fields that arise. Somehow, we can consider such a misfit as fitting a β particle of radius r +δr into a cavity of radius r in α, as depicted below, r +δr r r +δr + r r’=r +δr’ particle cavity δr δr With the mutual deformation of the two phases, the net radial strain: E = ≅ r' r The strain energy per volume as defined as C’E2 > 0, where C’ is the elastic constant of α and β (a coherent parameter of both the two phases) for nucleation of β in α (i.e., transformation α β). Then we have the net change of Gibbs free energy as expressed as: 4π 4π ΔG(r) = r3∆G + 4пr2 γ + rCE32' 3 V 3 d∆G(r) 2γ 2γ At r*, = 0 , r* = − 2 = − 2 dr r* (∆GV + C'E ) (−∆SV ∆T + C'E ) 2 Note, for T<Teq, ΔGV or -ΔSVΔT <0, but C’E >0. 2 So, at a T just below Teq, it is possible -ΔSVΔT + C’E >0, and then r*<0 (unphysical meaning!) --- implying that nucleation can’t occur. In other words, only when T<<Teq, i.e., sufficiently undercooled, so that 2 -ΔSVΔT + C’E ≤0 ; or (Sβ − Sα ) − (T − T ) + C’E2 ≤0; −∆S( T − T )' + CE2 ≤0 V eq V eq CE' 2 CE' 2 T − Teq ≤ ; T ≤ Teq + (note: ΔSV <0) ∆SV ∆SV 3 C'E 2 Or temperature of phase transformation defined as T’tr = Teq - ∆SV α—>β Teq E=0 Ttr’ E≠0 E≠0 Ttr” E=0 β—>α Teq Consider the reverse process, β—>α The sample was cooled below Ttr’ and is now fully transformed back into α. Upon heating above Teq, α nucleate in β-matrix. ()SSαβ− Now ΔGV = - (TT−< )0, as Teq <T, Sα − Sβ >0. V eq 2 Sα − Sβ The elastic energy β—>α transformation is C”E , and ΔSV = >0 V Similarly as discussed above for α—>β transformation, for β—>α transformation to occur, the system must be superheated, i.e., T >> Teq, so that 2 2 -ΔSVΔT + C’’E ≤0 ; or −∆SV( T − T eq ) + CE '' ≤0 , where C’’ is the elastic constant of α and β (a coherent parameter of both the two phases) for nucleation of α in β (i.e., transformation β α). For many cases, C’’ ≈ C’ CE'' 2 CE'' 2 T − Teq ≥ ; T ≥ Teq + (note: ΔSV >0) ∆SV ∆SV C"E 2 C"E 2 Or temperature of phase transformation defined as Ttr” = Teq + , Ttr” = Teq + > Teq ∆SV ∆SV This leads to a hysteresis in transformation cycle (diagram below): E 2 ΔTh =ΔT’ +ΔT” = (Teq - Ttr’) + (Ttr” - Teq) = Ttr” - Ttr’ = (C’ + C”) ∆SV 4 α β (heat flow) ΔTh Ttr’ Teq Ttr” Summary of homogeneous nucleation in solid: 1. When the nucleation phase has a different volume or shape than the matrix it replaces, elastic energy (∆GS) must be considered as part of the volumetric contribution to nucleation, as described 4π 4π 4π in the equation, ΔG(r) = r3∆G + 4πr2 γ + rCE32' = rG3 ()∆ +∆ G+4πr2 γ. 3 V 3 3 VS 2. The interfacial contribution (4πr2 γ) to the nucleation barrier dominates at small nucleus sizes, and 4π volumetric contributions ( rG3 ()∆ +∆ G) dominate at large nucleus sizes. The competition 3 VS between these two contributions can produce a complicated sequence of states for a developing phase, i.e., at small “r” the system may select a state that minimizes surface energy at the expense of elastic contribution, while at large “r”, the interfacial structure can change with concomitant increases in interfacial energy whenever such a change leads to overall decrease in the free energy (ΔG(r)) through a decrease of the volumetric contribution. The sequence of states may include changes in interfacial structure that relax elastic energy or even phase changes in the nuclei if less stable phases have similar interfacial energies. 3. Typically for solid state nucleation, elastic energy contribution dominates at small particles sizes and the interfacial energy can be reduced significantly by adopting a coherent structure. As the particle grows, elastic energy can be reduced by the introduction of misfit dislocations into the interface. Such interfacial dislocations transform a coherent interface into a semi-coherent interface at the expense of increased interfacial energy. 4. In supersaturated crystalline solutions (matrix), the particles of the new phase initially formed are generally coherent with the matrix, due to their lowest interfacial energy compared to the semi-coherent or incoherent interfaces. Coherent inclusions have an associated elastic strain energy that resists nucleation. This elastic strain energy is not easy to express with simple algebraic expressions, except for ideal spherical particles (as we treated above in this lecture). --- ref. Prof. Craig Carter and his book, Kinetics of Materials, 1st Ed., Wiley-Interscience, 2005. 5 .